Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
  • C10G11/10—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with stationary catalyst bed
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/90—Regeneration or reactivation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J38/00—Regeneration or reactivation of catalysts, in general
  • B01J38/02—Heat treatment
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J38/00—Regeneration or reactivation of catalysts, in general
  • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
  • B01J38/12—Treating with free oxygen-containing gas
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
  • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
  • C10G11/04—Oxides
  • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
  • C10G11/20—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert heated gases or vapours
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
  • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
  • C10G47/04—Oxides
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
  • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
  • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
  • C10G47/12—Inorganic carriers
  • C10G47/16—Crystalline alumino-silicate carriers
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1037—Hydrocarbon fractions
  • C10G2300/104—Light gasoline having a boiling range of about 20 - 100 °C
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1037—Hydrocarbon fractions
  • C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1037—Hydrocarbon fractions
  • C10G2300/1048—Middle distillates
  • C10G2300/1051—Kerosene having a boiling range of about 180 - 230 °C
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1037—Hydrocarbon fractions
  • C10G2300/1048—Middle distillates
  • C10G2300/1055—Diesel having a boiling range of about 230 - 330 °C
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1088—Olefins
  • C10G2300/1092—C2-C4 olefins
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/40—Characteristics of the process deviating from typical ways of processing
  • C10G2300/42—Hydrogen of special source or of special composition
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/70—Catalyst aspects
  • C10G2300/708—Coking aspect, coke content and composition of deposits
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/80—Additives
  • C10G2300/802—Diluents
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
  • C10G2400/20—C2-C4 olefins

Definitions

• the present invention generally relates to the production of light olefins.
• the present invention relates to the catalytic cracking of liquid hydrocarbons to form light olefins.
• Catalytic cracking often involves converting vacuum gas oil to high octane gasoline, light fuels and light olefins.
• a liquid oil stream is contacted with a catalyst, in a reactor, under a certain temperature and pressure to cause the oil to crack and produce lighter products.
• coke a carbonaceous material
• deposits on the catalyst As a result of the coke deposits on the catalyst, the catalyst becomes less effective or inactive—that is, the catalyst becomes spent.
• the spent catalyst is sent to a regenerator where the coke is removed from the catalyst by combusting the coke. The regenerated catalyst is then returned to the reactor.
• One type of catalytic cracking process involves the conversion of paraffinic hydrocarbons having end point ⁇ 350 °C into light olefins (e.g., C2 and C3 hydrocarbons).
• the conversion of paraffinic hydrocarbons having end point ⁇ 350 °C into light olefins requires high temperature (above 600 °C) and relatively short residence time to overcome the endothermicity of the reactions and prevent oligomerization of the light olefins.
• catalyst deactivation is problematic; specifically, catalysts in this process deactivate more frequently than some other catalytic processes. Catalyst deactivation is caused by coke formation and structural damage of the catalyst caused, at least in part, by high temperatures.
• ACOTM Advanced Catalytic Olefins
• Embodiments of the process involve alternately utilizing one of at least two trains of fixed bed reactors to catalytically crack hydrocarbons in a feed mixture that includes the hydrocarbons and dry gas. In this way, a continuous process involving cyclic regeneration of catalyst is provided, where minimal catalyst makeup is required because the dry gas serves as a diluent that minimizes coke formation and reduces catalyst structural damage.
• Embodiments of the invention include a method of producing olefins by a catalytic cracking process.
• the method may include providing a first train of fixed bed reactors and a second train of fixed bed reactors for processing a feed that comprises one or more paraffins.
• the method may also include alternating between the first train of fixed bed reactors and the second train of fixed bed reactors being in operation in the catalytic cracking process.
• the train of fixed bed reactors in operation may be adapted to contact the feed with a catalyst under reaction conditions sufficient to produce a reactor effluent that includes a C2 to C 4 olefin, dry gas, and liquid hydrocarbons.
• the dry gas may include one or more of methane, hydrogen, ethane, or propane.
• the method may also include recovering the C2 to C 4 olefin from the reactor effluent.
• the method may further include recirculating at least some of the methane and hydrogen of the dry gas as part of the feed to the train of fixed bed reactors in operation.
• wt.% refers to a weight, volume, or molar percentage of a component, respectively, based on the total weight, the total volume, or the total moles of material that includes the component.
• 10 moles of component in 100 moles of the material is 10 mol.% of component.
• Embodiment 1 is a method of producing olefins by a catalytic cracking process.
• the method includes the steps of providing a first train of fixed bed reactors and a second train of fixed bed reactors for processing a feed that contains one or more paraffins; alternating between the first train of fixed bed reactors and the second train of fixed bed reactors being in operation in the catalytic cracking process, wherein the train of fixed bed reactors in operation contacts the feed with a catalyst under reaction conditions sufficient to produce a reactor effluent that contains a C2 to C 4 olefin, dry gas, and liquid hydrocarbons, the liquid hydrocarbons containing unreacted hydrocarbons from the feed, the dry gas containing one or more of methane, hydrogen, ethane, or propane; recovering the C2 to C 4 olefin from the reactor effluent; and recirculating at least some of the methane and hydrogen of the dry gas as part of the
• Embodiment 2 is the method of embodiment, wherein the one or more paraffins have an end point of less than 350 °C.
• Embodiment 3 is the method of any of embodiments 1 and 2, wherein the feed is selected from the list consisting of: light naphtha, heavy naphtha, kerosene, and combinations thereof.
• Embodiment 4 is the method of any of embodiments 1 to 3, wherein the alternating includes: when the first train of fixed bed reactors is in operation, the second train of fixed bed reactors is being regenerated or is on standby, ready to be put in operation when the first train of fixed bed reactors is taken out of operation, and vice versa.
• Embodiment 5 is the method of any of embodiments 1 to 4, wherein a time for the alternating is determined by the condition of the catalyst of the train of fixed bed reactors in operation.
• Embodiment 6 is the method of any of embodiments 1 to 5, wherein catalyst beds of each of the trains of fixed bed reactors can be one type of catalyst to three different types of catalyst.
• Embodiment 7 is the method of any of embodiments 1 to 6, wherein the catalyst contains a zeolite based catalyst having medium pore size of 10-ring or large pore size pore of 12-ring.
• Embodiment 8 is the method of embodiment 7, wherein the zeolite based catalyst having medium pore size contains a catalyst selected from the list consisting of: MFI, MEL, MTT, MRE, MWW, FER, CGS, SVR and STW.
• Embodiment 9 is the method of embodiment 7, wherein the zeolite based catalyst having large pore size contains a catalyst selected from the list consisting of: MOR, FAU, BOG, MTW, MAZ, OFF, BEA, MEI, LTL, and GME.
• Embodiment 10 is the method of any of embodiments 7 to 9, wherein the zeolite based catalyst contains a selection from the list consisting of: 60 wt.
• Embodiment 11 is the method of any of embodiments 1 to 10, wherein the reactor temperature range is in a range from 450 to 900 °C, preferably from 530 to 800 °C and more preferably from 580 to 750 °C.
• Embodiment 12 is the method of any of embodiments 1 to 11, wherein, the reactor temperature is a temperature above 450 °C.
• Embodiment 13 is the method of any of embodiments 1 to 12, wherein the reactor pressure range is from vacuum to 10 bars, preferably from vacuum to 5 bars.
• Embodiment 14 is the method of any of embodiments 1 to 13, wherein the reactor WHSV range is from 1 to 80 hr "1 , preferably from 2 to 70 hr "1, and more preferably from 4 to 50 hr "1 .
• Embodiment 15 is the method of any of embodiments 1 to 14, wherein each of the trains of fixed bed reactors can have from one reactor to seven reactors.
• Embodiment 16 is the method of any of embodiments 1 to 15, wherein the feed contains a dry gas/ hydrocarbon feed ratio in the range 0 to 10 by wt., preferably from 0 to 5 by wt.
• Embodiment 17 is the method of any of embodiments 1 to 16, wherein the dry gas primarily contains methane and/or hydrogen.
• Embodiment 18 is the method of any of embodiments 1 to 17, wherein the dry gas further contains ethylene and/or ethane.
• Embodiment 19 is the method of embodiment 1 to 18, wherein the dry gas contains less than 0.5 wt. % ethylene.
• Embodiment 20 is the method of any of embodiments 1 to 19, wherein when the first reactor train or second reactor train contains a plurality of reactors, the plurality of reactors are in series in the first reactor train or second reactor train.
• FIG. 1 shows a system for producing olefins by a catalytic cracking process, according to embodiments of the invention
• FIG. 2 shows a method of producing olefins by a catalytic cracking process, according to embodiments of the invention
• FIG. 3 shows a graph of ethylene and propylene yields as a function of time on stream in the catalytic cracking of light naphtha in the absence of steam in a fixed bed reactor
• FIG. 4 shows X-ray diffraction (XRD) spectrum of zeolite catalyst after three cycles.
• the process includes the use of two or more trains of reactors arranged in parallel to ensure a continuous mode of operation, including during catalyst regeneration.
• the process further includes using dry gas to dilute the hydrocarbon feed to protect catalyst activity.
• Embodiments of the process produces light olefins from liquid hydrocarbons using a cyclic regenerative process (cyclic fixed bed reactors configuration) where the liquid hydrocarbon feed is introduced to a first train of fixed bed reactors for catalytic cracking while a second train of fixed bed reactors is in a standby mode or is in the process of having its catalyst regenerated.
• the liquid hydrocarbon feed in embodiments, may be diluted with dry gas.
• the dry gas may be recycled from the effluent of the catalytic cracking process.
• liquid hydrocarbon feed has an end point ⁇ 350 °C. The discovered process requires minimal catalyst makeup because the dry gas serves as a diluent, which minimizes coke formation and reduces catalyst structural damage.
• FIG. 1 shows system 10 for producing olefins by a catalytic cracking process, according to embodiments of the invention.
• hydrocarbon feed 101 may be supplied to system 10 from other refinery processes such as distillation processes.
• Hydrocarbon feed 101 may include one or more liquid streams of light naphtha, heavy naphtha, kerosene, diesel or combinations thereof.
• Hydrocarbon feed 101 may comprise primarily paraffins.
• dry gas feed 102 may be supplied to system 10.
• dry gas feed 102 may originate from other refinery processes. As shown in FIG. 1, however, dry gas feed 102 is a recycled stream from the catalytic cracking process carried out by system 10.
• dry gas feed 102 may be a combination of dry gas from another refinery process and dry gas from the catalytic cracking process.
• dry gas feed 102 may include one or more of methane, ethane, hydrogen, propane, or ethylene. Dry gas feed 102 may include primarily methane. Dry gas feed 102 may include primarily methane and hydrogen. In embodiments of the invention, dry gas feed 102 may include less than 0.5 wt. % ethylene.
• combined feed stream 103 includes a dry gas/hydrocarbon feed ratio by weight in the range 0 to 10, and all ranges and values there between including 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10, preferably from 0 to 5 and more preferably from 0.1 to 3.
• dry gas feed 102 dilutes hydrocarbon feed 101. Diluting hydrocarbon feed 101 in this way minimizes coke formation in the catalytic cracking process, reduces catalyst structure damage, and allows the catalyst to be subjected to more favorable conditions for catalytic activity.
• hydrocarbon feed 101 which is supplied to system 10 is diluted to form combined feed stream 103, which is heated to form heated feed stream 104, which are channeled as heated feed stream 105 or heated feed stream 106, which are then heated to form heated feed stream 107 or heated feed stream 108, which are fed to reactor train 121 and reactor train 122, respectively, depending on which reactor train is in operation.
• Diluting hydrocarbon feed 101 in this way to supply reactor train 121 and reactor train 122 reduces coke formation rate in reactor train 121 and reactor train 122 by operating at controlled hydrocarbon partial pressure.
• dry gas feed 102 to carry out the dilution avoids the use of steam for that purpose and thereby avoids catalyst structural damage by steam diluent. Because catalyst structural damage may be avoided in embodiments of the invention where dry gas is used as feed diluent, no fresh catalyst is needed to be added to the reactors to maintain product yield.
• Combined feed stream 103 may be preheated in heat exchanger 117. As shown in FIG. 1, system 10 utilizes reactor effluent 113 to heat combined feed stream 103. In embodiments of the invention, combined feed stream 103 is heated to a temperature in the range 25 to 350 °C to form heated feed stream 104. Splitter 118 may direct heated feed stream 104 as heated feed stream 105 or heated feed stream 106, towards the reactor system, depending on which of reactor train 121 (R-TRAIN1) and reactor train 122 (R-TRAIN2) is in operation.
• R-TRAIN1 reactor train 121
• R-TRAIN2 reactor train 122
• heated feed stream 105 may be heated further by heater 119 to form heated feed stream 107.
• Heated feed stream 107 is then routed to reactor train 121.
• Heated feed stream 107 may have a temperature in the range of 500 to 750 °C and a pressure in the range of 1 to 5 bars when entering reactor train 121.
• Reactor train 121 catalytically cracks hydrocarbons of heated feed stream 107 to form reactor effluent 111, which may comprise light olefins such as C2 to C 4 olefins, dry gas, and other hydrocarbons.
• the reactor train may have up to 7 reactors connected in series or parallel or a combination of both configurations.
• reactor effluent 111 may include one or more of methane, hydrogen, ethane, or propane. Reactor effluent 111 may be channeled by element 123 as reactor effluent 113, towards heat exchanger 117.
• reactor train 122 while reactor train 121 is in operation, reactor train 122 is having its catalyst regenerated or is on standby.
• the catalyst of reactor train 122 may be regenerated by passing air stream 110 to heater 120, where air stream 110 may be heated. After being heated, air stream 110 may be flowed through each reactor of reactor train 122 burn off the carbon deposits (coke) that are on the catalysts in the reactors.
• air stream 110 is flowed to reactor train 122 only when the catalyst of reactor train 122 is being regenerated. After completing the regeneration process, reactor train 122 may be placed on standby.
• reactor train 122 is put back in operation when reactor train 121 is taken out of service to have the catalyst of reactor train 121 regenerated.
• a time for the alternating between reactor train 121 and reactor train 122 is determined by the condition of the catalyst of whichever of reactor train 121 and reactor train 122 is in operation.
• heated feed stream 106 may be further heated by heater 120 to form heated feed stream 108.
• Heated feed stream 108 is then routed to reactor train 122.
• Heated feed stream 108 may have a temperature in the range of 500 to 750 °C and a pressure in the range of 1 to 5 bars when entering reactor train 122.
• Reactor train 122 catalytically cracks hydrocarbons of heated feed stream 108 to form reactor effluent 112, which may comprise light olefins such as C2 to C 4 olefins, dry gas, and other hydrocarbons.
• the reactor train may have up to 7 reactors connected in series or parallel or a combination of both configurations.
• a fired furnace exists between each reactor.
• reactor effluent 112 may include one or more of methane, hydrogen, ethane, or propane.
• Reactor effluent 112 may be channeled by element 123 as reactor effluent 113, towards heat exchanger 117.
• reactor train 122 while reactor train 122 is having its catalyst regenerated or is on standby.
• the catalyst of reactor train 121 may be regenerated by passing air stream 109 to heater 119, where air stream 109 may be heated. After heating, air stream 109 may be flowed through each reactor of reactor train 121 to burn off the carbon deposits (coke) on the catalysts in the reactors.
• air stream 109 is flowed to reactor train 121 only when the catalyst of reactor train 121 is being regenerated. After completing the regeneration process, reactor train 121 may be placed on standby. Eventually, reactor train 121 is put back in operation when reactor train 122 is taken out of service to have catalyst of reactor train 122 regenerated.
• the cyclic regenerative process implemented by system 10, provides a catalytic cracking operation that is alternated between reactor train 121 and reactor train 122.
• reactor train 121 is catalytically cracking hydrocarbons to produce light olefins and other products
• reactor train 122 is being regenerated or is on standby and vice versa.
• reactor train 122 is ready to be put in operation when reactor train 121 needs to be taken out of operation and vice versa.
• reactor train 122 may be immediately put into operation and vice versa.
• system 10 could have more than two trains of reactors, e.g., system 10 could have two, three, four, five, six or seven trains of reactors.
• Each of reactor train 121 and reactor train 122 may have one or more reactors.
• each of reactor train 121 and reactor train 122 may each have one, two, three, four, five, six, or seven reactors.
• the reactors may be arranged in series or parallel, or combinations thereof, within the respective reactor train.
• the catalyst used in reactor train 121 and reactor train 122 include a zeolite based catalyst having medium pore size such as one or more of: MFI, MEL, MTT, *MRE, MWW, FER, CGS, SVR, or STW.
• the catalyst used in reactor train 121 and reactor train 122 include zeolite based catalyst having large pore size such as one or more of: MOR, FAU, BOG, MTW, MAZ, OFF, *BEA, MEI, LTL, or GME.
• the medium pore size zeolite catalyst may have 10-ring pores and the large pore size zeolite catalyst may have 12-ring pores.
• the catalyst used in reactor train 121 and reactor train 122 may include a zeolite based catalyst that comprises one or more of: phosphorous, alkaline, alkaline earth metals, transition metals, or rare earth metals.
• the catalyst beds of each of reactor train 121 and reactor train 122 can have a plurality of different catalysts.
• reactor train 121 and reactor train 122 may each have one, two, or three different catalysts. Different reactors in reactor train 121 and reactor train 122 may have different catalysts.
• the zeolite based catalyst used in reactor train 121 and reactor train 122 contains zeolite, filler, binder, promotors and matrix components.
• the final cracking catalyst may contain up to 60 wt. % of zeolite.
• the reaction conditions sufficient to produce reactor effluent 1 1 1 and reactor effluent 1 12 may include one or more reactors of reactor train 121 and reactor train 122 having a reactor temperature above 450 °C.
• the reaction conditions sufficient to produce reactor effluent 1 1 1 or reactor effluent 1 12 may include one or more reactors of reactor train 121 and reactor train 122 having a reactor temperature in the range from 450 to 900 °C, and all ranges and values there between including 450 °C to 500 °C, 500 °C to 550 °C, 550 °C to 600 °C, 600 °C to 650 °C, 650 °C to 700 °C, 700 °C to 750 °C, 750 °C to 800 °C, 800 °C to 850 °C, and 850 °C to 900 °C, preferably from 530 °C to 800 °C, and more preferably from
• the reaction conditions sufficient to produce reactor effluent 1 1 1 and reactor effluent 1 12 may include one or more reactors of reactor train 121 and reactor train 122 having a reactor pressure in the range from vacuum to 10 bars, and all ranges and values there between including vacuum, 1 bars, 2, bars, 3 bars, 4 bars, 5 bars, 6 bars, 7 bars, 8 bars, 9 bars, and 10 bars, preferably from vacuum to 5 bars.
• the reaction conditions sufficient to produce reactor effluent 1 1 1 and reactor effluent 1 12 may include one or more reactors of reactor train 121 or reactor train 122 having a reactor WHSV range is from 1 to 80 hr "1 , and all ranges and values there between including 1 hr "1 to 5 hr “1 , 5 hr “1 to 10 hr “1 , 10 hr “1 to 15 hr “1 , 15 hr “1 to 20 hr “1 , 20 hr “1 to 30 hr “1 , 30 hr “1 to 40 hr “1 , 40 hr “1 to 50 hr “1 , 50 hr “1 to 60 hr “1 , 60 hr “1 to 70 hr “1 , and 70 hr “1 to 80 hr “1 , preferably from 2 to 70 hr “1 , preferably from 5 to 55 hr "1 ,
• Reactor effluent 1 1 1 and 1 12 may be routed, as reactor effluent 1 13, to heat exchanger 1 17 where reactor effluent 1 13 is cooled and combined feed stream 103 is heated. Reactor effluent 1 13 is cooled to form cooled reactor effluent stream 1 14, which may be routed to separator 124 for separation into a variety of targeted products such as light olefins 126 (e.g., d to CA olefins), dry gas feed 102, and other hydrocarbons 125. Separator 124 may include a series of separation equipment. Unconverted feed of other hydrocarbons 125 can be recycled back with hydrocarbon feed 101 to reactor train 121 and reactor train 122 for further conversion.
• light olefins 126 e.g., d to CA olefins
• Separator 124 may include a series of separation equipment. Unconverted feed of other hydrocarbons 125 can be recycled back with hydrocarbon feed 101 to reactor train 121 and reactor train
• FIG. 2 shows method 20 for producing olefins by a catalytic cracking process, according to embodiments of the invention.
• Method 20 may begin at block 200, which involves providing a first train of fixed bed reactors (e.g., reactor train 121, FIG. 1) and a second train of fixed bed reactors (e.g., reactor train 122, FIG.
• Method 20 may also include, at block 201, alternating between reactor train 121 and reactor train 122 being in operation in the catalytic cracking process. Whichever of reactor train 121 and reactor train 122 that is in operation contacts hydrocarbon feed 101 (as part of heated feed stream 107 and heated feed stream 108) with a catalyst under reaction conditions sufficient to produce a reactor effluent 1 1 1 or reactor effluent 1 12 that includes one or more C2 to C 4 olefins, dry gas, and liquid hydrocarbons (including unreacted hydrocarbons of the feed).
• the dry gas may include one or more of methane, hydrogen, ethane, or propane.
• Method 20 may further include, at block 202, regenerating the catalyst that is not in operation.
• Block 203 includes, after the catalyst of the reactor train that is not in operation is regenerated, keeping the regenerated reactor train on standby mode to replace the reactor train in operation when the reactor train in operation needs regenerating.
• Block 204 involves recovering the one or more C2 to C4 olefins from the reactor effluent.
• block 205 includes recirculating at least some of the methane and hydrogen of the dry gas as part of feed to whichever of reactor train 121 and reactor train 122 that is in operation.
• Example 1 [0046] In Example 1, a test was carried out in which naphtha was cracked catalytically over fixed bed reactor and fluidized bed reactor pilot plant.
• the naphtha feed had the following composition (Table 1):
• Example 1 a catalyst was tested for light naphtha cracking using fixed bed reactor and fluidized bed pilot plant. Reactor temperature, flow rate and steam rate are provided in Table 2. Residence time of the fixed bed and the fluidized bed pilot plant was 10 minutes and less than a minute, respectively. The fixed bed had the flexibility to vary the residence time unlike fluid catalytic cracking (FCC) type process, where the residence time was limited to below a minute. As can be seen, in Table 2, the yield toward light olefin is higher by approximately 10% when a fixed bed is used.
• FCC fluid catalytic cracking
• Example 2 the light naphtha feed was cracked in the absence of steam in a fixed bed reactor.
• the reaction was at a temperature of 650 °C, a pressure of 3 bars, and a WHSV of 40 hr "1 .
• the catalyst used was a modified ZSM-5 mixed with binder and filler.
• the product yields of light olefins and aromatics were 37 wt. % and 6 wt. %.
• the yields of methane, ethane and propane were 3.4 wt. %, 4.6 wt. %, and 7 wt. %, respectively.
• the unconverted feed was 40 wt. %.
• the remaining portions were naphthene and higher olefins.
• Example 3 the light naphtha feed was cracked in the absence of steam in a fixed bed reactor at a temperature of 600 °C, a pressure of 4 bars, and WHSV of 40 hr "1 .
• the catalyst contained less than 35 wt. % zeolite.
• the products yields were recorded at different time on stream.
• the ethylene and propylene yields are shown in FIG. 3, which show substantially constant or constant values over the 11 hours recorded.
• Example 4 the catalyst stability was evaluated using X-ray diffraction
• FIG. 4 shows the XRD spectrum of the zeolite catalyst after three cycles (where one cycle is: reaction then regeneration). The reaction temperature was 650 °C and the regeneration was conducted at 550 °C. The catalyst maintained its crystallinity when compared to fresh catalyst. This indicates that the catalyst structure is maintained and no sign of structure damage was observed.

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